JPH041155A - Production of fatty acid halogenide - Google Patents

Abstract

PURPOSE: To rapidly and effectively execute the phase separation by adding a fatty acid nitrogen derivative to a reaction mixture of a fatty acid and a halogenating agent when the subject compound is prepared by reacting the reaction mixture and separating the phases.

CONSTITUTION: A saturated or unsaturated 2-24C, preferably 12-24C fatty acid is reacted with a halogenating agent, preferably a phosphorus halide (particularly phosphorus trichloride), at 40-70°C, optionally followed by hydrolysis of the excess halogenating agent, then 0.01-0.5 wt.%, particularly 0.05-0.2 wt.% on the basis of the weight of the fatty acid starting material, of a fatty acid nitrogen derivative (for example; fatty nitrile, fatty amine, fatty amide) is added to the reaction mixture, and then the fatty acid halogenide upper layer is separated from the inorganic lower layer. The fatty acid nitrogen derivative is preferably added to the fatty acid before the reaction with the halogenating agent.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to an improved method for producing halogenated fatty acids (fatty acid halogenides), particularly chlorinated fatty acids. Fatty acid halogenides, especially chlorinated fatty acids, are expensive commercially available and alkylketene dimers (
AKD) is often used in the production of [0002]

[Conventional technology]

Traditionally, chloric acid is prepared by reacting a fatty acid with a chlorinating agent such as ternary, ternary, or thionyl chloride, and then separating the resulting fatty acid halide from the inorganic material. has been manufactured. [0003] West German Patent Application Publication Specification No. 1 280 854 [WE
B Leuna-Werke (VEB Leuna-Werke)
ke) ”Walter Ulbricht
Ulbricht)''], the fatty acid and the excess ternary mixture were heated at 40 to 80°C in one or more reactors.
It is known to carry out the reaction at a temperature of 10 to 140 minutes and to transfer the reaction product to a separation vessel where the upper chlorinated fatty acid layer is separated from the lower phosphorous acid layer. The upper chlorinated fatty acid layer also contains unreacted ternary neighbors. [0004] U.S. Patent No. 2,262,431 [Armor &
According to Armor & Co., after the reaction of the fatty acid with the halogen, the unreacted halogen is hydrolyzed with water to form phosphoric acid or phosphorous acid without affecting the halogenated fatty acid. and thereby obtain a substantially pure fat halide upper layer. [0005]

[Problem to be solved by the invention]

One of the problems encountered when producing halogenated fatty acids on a commercial scale is that the separation of halogenated fatty acids from inorganic materials is often difficult due to the setting of two layers, inter alia This means that it takes time for emulsification to occur. [0006] What is required for operation on a practical scale is to quickly separate and clarify within 6 hours, preferably within 3 hours, and to form a clear interface, and then to efficiently remove the underlying inorganic layer. This means that it is possible to remove. [0007]

[Means to solve the problem]

The present invention therefore provides a method for producing halogenated fatty acids, comprising reacting a fatty acid with a halogenating agent, then optionally hydrolyzing the unreacted halogenating agent, and adding a fatty acid nitrogen derivative to the reaction mixture. By adding a halogenated fatty acid upper layer from an inorganic lower layer. [0008] We describe a process carried out in the presence of at least 0.5 mole % of a carboxamide, such as hydrochlorinated dimethyl formaldehyde, in US Pat. No. 4,900,479 [Freudenberg et al.
enberg)/BASF]. The present invention differs from this US patent in that it uses fatty acid nitrogen derivatives. [0009] Certain low-quality fatty acids, such as those produced from crude tallow, contain small amounts of fatty acid amines as well as many impurities such as amides, alcohols, alkanes, color bodies, and others. . Of course, excellent quality chlorinated fatty acids cannot be obtained from such low quality fatty acids. The invention therefore provides particularly high quality chlorinated fatty acids, i.e. less than 0.5% by weight, preferably 0.5% by weight of non-saponifiable substances. The aim is to produce less than 3% by weight, so the fatty acid starting material must also have a similar degree of purity. [0010] The method according to the present invention provides a method for producing saturated or unsaturated C2-C2
4, in particular using C12 to C24 fatty acids as starting materials to obtain fatty halides of the same chain length. [0011] The halogenating agent used in a preferred embodiment of the present invention is halogen-neighboring, preferably ternary-neighboring. [0012] 0.0 based on the weight of fatty acid starting material in the reaction mixture
Preferably, 1 to 0.5% by weight of the fatty acid nitrogen derivative is added, more preferably 0.05 to 0.2% by weight. Fatty acid nitrogen derivatives are soluble in fatty acids at such concentrations. Fatty acid nitrogen derivatives include fatty nitriles, primary, secondary,
Alternatively, it can be selected from tertiary amines, diamines, quaternary ammonium salts, fatty amine oxides, mono- or disubstituted fatty amines, and the like. As fatty amides, compounds containing 2 to 44, preferably 10 to 36 carbon atoms, in particular primary amides containing 4 to 24, preferably 12 to 24 carbon atoms, or containing 24 to 44 carbon atoms; Preferably, secondary amides are used. Similar chain lengths are also preferred when using fatty amines and other fatty acid nitrogen derivatives. [0013] From a processing point of view, it is advantageous to add a fatty acid nitrogen derivative to the fatty acid before reacting with the halogenating agent. [0014] The reaction of the fatty acid with the halogenating agent is preferably carried out in one or more reactors at a temperature of 40 to 70°C and a residence time of 10 to 140 minutes. The reaction product is preferably subsequently transferred to a separation vessel where the upper halogenated fatty acid layer is separated from the lower inorganic layer. [0015] The halogen is preferably used in a molar excess relative to the fatty acid. After the reaction of the fatty acid with the halogen neighbor, the unreacted halogen neighbor can be hydrolyzed with water to phosphoric acid or phosphorous acid without affecting the halogenated fatty acid, thereby producing a substantially pure phosphorous acid. A top layer of fatty halides can be obtained. According to the invention, the separation of the reaction mixture into two layers is considerably facilitated, usually resulting in a sharp interface and a clear to slightly cloudy upper layer. Therefore, the present invention provides faster processing speeds in existing equipment. The inorganic lower layer is then separated to yield substantially pure halogenated fatty acids. The invention also makes it possible to produce halogenated fatty acids from pure starting materials containing 0.1 to 0.3% of non-saponifiable substances with good and fast phase separation. [0016]

【Example】

The fatty acid was heated to 65-70°C with stirring. The triadic ratio (1.5 molar excess calculated based on fatty acids) is 15
Added over a period of minutes. After the addition, the reaction mixture was stirred for an additional 30 minutes. The reaction mixture was allowed to settle at reaction temperature. [0017] The upper layer was slightly cloudy. Separation/clarification point (separa
tion/clarification point)
The upper layer of chlorinated fatty acids, with a clear interface,
It is defined as when it becomes completely transparent. [0018] The results are summarized in the table below. (J Kaiju4-11t)t) (/J [0019] Fatty acid clearing time (hours) Additive (HCD-HD) (0°05%) 0M blend (HCD+HD) 3° (Oo 05%) 0M blend (HCD + HD) (0°05%) 0M Blend <HCD) 1° (0°2%) [00201 T2 and T6 are respectively British standard (British 5
tallow 2 and tallow 6 as defined in Standard) 3919 (1987)
(tallow 6). O
M represents oleylamide and X represents N-phenylethylstearamide. H represents the hydrogenated starting fatty acid, C the starting fatty acid crystallized from methanol, and D the distilled starting fatty acid, all containing 0.1 to 0.2% by weight of unsaponifiable material. [0021] Similar beneficial effects were obtained when oleylamide was replaced with oleylamine or stearylamine.

Claims (10)

[Claims] 1. A method for producing halogenated fatty acids by reacting a fatty acid with a halogenating agent and separating an upper layer of the halogenated fatty acid from an inorganic lower layer, the method comprising adding a fatty acid nitrogen derivative to the reaction mixture. A method characterized by: Claim 2: The fatty acid is saturated or unsaturated C_2 to C
2. The method of claim 1, wherein the fatty acid is a _2_4 fatty acid. 3. The method of claim 1, wherein the halogenating agent is a phosphorus halide. 4. The method according to claim 1, wherein a fatty acid nitrogen derivative is added to the fatty acid before reacting with the halogenating agent. 5. The method of claim 1, wherein the fatty acid starting material contains less than 0.5% by weight of non-saponifiable material. Claim 6: 0.02 based on the weight of fatty acid starting material
2. The method of claim 1, wherein between 0.5% and 0.5% by weight of fatty acid nitrogen derivatives are added to the reaction mixture. 7. The fatty acid nitrogen derivative is a fatty nitrile, a
, secondary or tertiary amines, diamines, quaternary ammonium salts, fatty amine oxides, mono- or disubstituted fatty amines, and the like. 8. The method of claim 1, wherein the fatty acid nitrogen derivative is a fatty amide having 2 to 44 carbon atoms. 9. Claim 8, wherein the fatty amide is a primary amide.
the method of. 10. The method of claim 8, wherein the fatty amide is a secondary amide.